Determination of Kinetic Parameters and Identification of the Rate-Determining Steps in the Oxygen Exchange Process for LaNi(0.6)Fe(0.4)O(3−δ)

The mixed ionic and electronic oxide LaNi(0.6)Fe(0.4)O(3−δ) (LNF) is a promising ceramic cathode material for solid oxide fuel cells. Since the reaction rate of oxygen interaction with the cathode material is extremely important, the present work considers the oxygen exchange mechanism between O(2) and LNF oxide. The kinetic dependence of the oxygen/oxide interaction has been determined by two isotopic methods using (18)O-labelled oxygen. The application of the isotope exchange with the gas phase equilibrium (IE-GPE) and the pulsed isotope exchange (PIE) has provided information over a wide range of temperatures (350–800 °C) and oxygen pressures (10–200 mbar), as each method has different applicability limits. Applying mathematical models to treat the kinetic relationships, the oxygen exchange rate (r(H), atom × cm(−2) × s(−1)) and the diffusion coefficient (D, cm(2)/s) were calculated. The values of r(H) and D depend on both temperature and oxygen pressure. The activation energy of the surface exchange rate is 0.73 ± 0.05 eV for the PIE method at 200 mbar, and 0.48 ± 0.02 eV for the IE-GPE method at 10–20 mbar; for the diffusion coefficient, the activation energy equals 0.62 ± 0.01 eV at 10–20 mbar for the IE-GPE method. Differences in the mechanism of oxygen exchange and diffusion on dense and powder samples are observed due to the different microstructure and surface morphology of the samples. The influence of oxygen pressure on the ratio of contributions of different exchange types to the total oxygen exchange rate is demonstrated. For the first time, the rate-determining step in the oxygen exchange process for LNF material has been identified. This paper discusses the reasons for the difference in the mechanisms of oxygen exchange and diffusion.